Process for producing polymers

ABSTRACT

This invention provides a compositions that are useful for polymerizing at least one monomer into at least one polymer.

FIELD OF THE INVENTION

[0001] This invention is related to the field of compositions that canbe used to polymerize monomers into at least one polymer.

BACKGROUND OF THE INVENTION

[0002] The production of polymers is a multi-billion dollar business.This business produces billions of pounds of polymers each year.Millions of dollars have been spent on developing technologies that canadd value to this business.

[0003] One of these technologies is called metallocene catalysttechnology. Metallocene catalysts have been known since about 1960,however, their low productivity did not allow them to be commercialized.About 1975, it was discovered that contacting one part water with twoparts trimethylaluminum to form methyl aluminoxane, and then contactingsuch methyl aluminoxane with a metallocene compound, formed ametallocene catalyst that had greater activity. However, it was soonrealized that large amounts of expensive methyl aluminoxane were neededto form an active metallocene catalyst. This has been a significantimpediment to the commercialization of metallocene catalysts.

[0004] Borate compounds have been use in place of large amounts ofmethyl aluminoxane. However, this is not satisfactory, since boratecompounds are very sensitive to poisons and decomposition, and can alsobe very expensive.

[0005] It should also be noted that having a heterogeneous catalyst isimportant. This is because heterogeneous catalysts are required for mostmodern commercial polymerization processes. Furthermore, heterogeneouscatalysts can lead to the formation of substantially uniform polymerparticles that have a high bulk density. These types of substantiallyuniformed particles are desirable because they improve the efficiency ofpolymer production and transportation. Efforts have been made to produceheterogeneous metallocene catalysts, however, these catalysts have notbeen entirely satisfactory.

[0006] Therefore, the inventors provide this invention to solve theseproblems.

SUMMARY OF THE INVENTION

[0007] An object of this invention is to provide a process that producesa composition that can be used to polymerize monomers into at least onepolymer.

[0008] Another object of this invention is to provide said composition.

[0009] Another object of this invention is to provide a process topolymerize monomers into at least one polymer using said composition.

[0010] Another object of this invention is to provide a manufacture thatcomprises at least one said polymer.

[0011] Another object of this invention is to provide a machine thatcomprises at least one said manufacture.

[0012] In accordance with one embodiment of this invention, a process toproduce a composition of matter is provided. Said process comprises (oroptionally, consists essentially of, or consists of) contacting anorganometal compound, a treated solid oxide compound, and anorganoaluminum compound to produce said composition, wherein saidcomposition consists essentially of (or optionally, consists of) apost-contacted organometal compound, a post-contacted treated solidoxide compound, and optionally, a post-contacted organoaluminumcompound.

[0013] In accordance with another embodiment of this invention, acomposition of matter is provided. Said composition consists essentiallyof a post-contacted organometal compound, a post-contacted treated solidoxide compound, and optionally, a post-contacted organoaluminumcompound.

[0014] In accordance with another embodiment of this invention, aprocess to polymerize monomers into at least one polymer using saidcomposition is provided. Said process comprises contacting saidcomposition with monomers.

[0015] In accordance with another embodiment of this invention amanufacture is provided. Said manufacture comprises at least one saidpolymer.

[0016] In accordance with another embodiment of this invention a machineis provided. Said machine comprises at least two said manufactures.

[0017] These objects, and other objects, will become more apparent tothose with ordinary skill in the art after reading this disclosure.

[0018] It should be noted that the phrase “consisting essentially of ”means that the only other items (such as, for example, process steps,and other compounds) included within the scope of the claims are thoseitems that do not materially affect the basic and novel characteristicsof the claimed invention.

[0019] It should also be noted that the phrase “consisting of ” meansthat the no other items (such as, for example, process steps, and othercompounds) are included within the scope of the claims, except itemsthat are impurities ordinarily associated with a composition, or itemsthat are process steps ordinarily associated with a process.

DETAILED DESCRIPTION OF THE INVENTION

[0020] Organometal compounds used in this invention have the followinggeneral formula.

FORMULA ONE: (X¹)(X²)(X³)(X⁴)M¹

[0021] In this formula, M¹ is selected from the group consisting oftitanium, zirconium, and hafnium. Currently, it is most preferred whenM¹ is zirconium.

[0022] In this formula (X¹) is independently selected from the groupconsisting of (hereafter “Group OMC-I ” ) cyclopentadienyls, indenyls,fluorenyls, substituted cyclopentadienyls, substituted indenyls, suchas, for example, tetrahydroindenyls, and substituted fluorenyls, suchas, for example, octahydrofluorenyls.

[0023] The substituents on the substituted cyclopentadienyls,substituted indenyls, and substituted fluorenyls, can be aliphaticgroups, cyclic groups, combinations of aliphatic and cyclic groups, andorganometallic groups, as long as these groups do not substantially, andadversely, affect the polymerization activity of the composition.Additionally, hydrogen can be a substituent.

[0024] Suitable examples of aliphatic groups are hydrocarbyls, such as,for example, paraffins and olefins. Suitable examples of cyclic groupsare cycloparaffins, cycloolefins, cycloacetylenes, and arenes.Additionally, alkylsilyl groups where each alkyl contains 1-12 carbonatoms, alkyl halide groups where each alkyl contains 1-12 carbon atoms,or halides, can also be used.

[0025] Suitable examples of such substituents are methyl, ethyl, propyl,butyl, tert-butyl, isobutyl, canyl, isoamyl, hexyl, cyclohexyl, heptyl,octyl, nonyl, decyl, dodecyl, 2-ethylhexyl, pentenyl, butenyl, phenyl,chloro, bromo, and iodo.

[0026] In this formula (X³) and (X⁴) are independently selected from thegroup consisting of (hereafter “Group OMC-II” ) halides, aliphaticgroups, cyclic groups, combinations of aliphatic and cyclic groups, andorganometallic groups, as long as these groups do not substantially, andadversely, affect the polymerization activity of the composition.

[0027] Suitable examples of aliphatic groups are hydrocarbyls, such as,for example, paraffins and olefins. Suitable examples of cyclic groupsare cycloparaffins, cycloolefins, cycloacetylenes, and arenes.Currently, it is preferred when (X³) and (X⁴) are selected from thegroup consisting of halides and hydrocarbyls, where such hydrocarbylshave from 1 to 10 carbon atoms. However, it is most preferred when (X³)and (X⁴) are selected from the group consisting of fluoro, chloro, andmethyl.

[0028] In this formula, (X²) can be selected from either Group OMC-I orGroup OMC-II.

[0029] When (X²) is selected from Group OMC-I, it should be noted that(X¹) and (X²) can be joined with a bridging group, such as, for example,aliphatic bridging groups, cyclic bridging groups, combinations ofaliphatic and cyclic bridging groups, and organometallic bridginggroups, as long as the bridging group does not substantially, andadversely, affect the polymerization activity of the composition.

[0030] Suitable examples of aliphatic bridging groups are hydrocarbyls,such as, for example, paraffins and olefins. Suitable examples of cyclicbridging groups are cycloparaffins, cycloolefins, cycloacetylenes, andarenes. Additionally, it should be noted that silicon and germanium arealso good bridging units.

[0031] Various processes are known to make these compositions. See, forexample, U.S. Pat. Nos. 4,939,217; 5,210,352; 5,436,305; 5,401,817;5,631,335, 5,571,880; 5,191,132; 5,480,848; 5,399,636; 5,565,592;5,347,026; 5,594,078; 5,498,581; 5,496,781; 5,563,284; 5,554,795;5,420,320; 5,451,649; 5,541,272; 5,705,478; 5,631,203; 5,654,454;5,705,579; and 5,668,230; the entire disclosures of which are herebyincorporated by reference.

[0032] Specific examples of such compositions are as follows:

[0033] bis(cyclopentadienyl) hafnium dichloride;

[0034] bis(cyclopentadienyl) zirconium dichloride;

[0035] [ethyl(indenyl)₂] hafnium dichloride;

[0036] [ethyl(indenyl)₂] zirconium dichloride;

[0037] [ethyl(tetrahydroindenyl)₂] hafnium dichloride;

[0038] [ethyl(tetrahydroindenyl)₂] zirconium dichloride;

[0039] bis(n-butylcyclopentadienyl) hafnium dichloride;

[0040] bis(n-butylcyclopentadienyl) zirconium dichloride;

[0041] ((dimethyl)(diindenyl) silane) zirconium dichloride;

[0042] ((dimethyl)(diindenyl) silane) hafnium dichloride:

[0043] ((dimethyl)(ditetrahydroindenyl) silane) zirconium dichloride;

[0044] ((dimethyl)(di(2-methyl indenyl)) silane) zirconium dichloride;and

[0045] bis(fluorenyl) zirconium dichloride.

[0046] Organoaluminum compounds have the following general formula.

FORMULA TWO: Al(X⁵)_(n)(X⁶)_(3−n)

[0047] In this formula (X⁵) is a hydrocarbyl having from 1-20 carbonatoms. Currently, it is preferred when (X⁵) is an alkyl having from 1 to10 carbon atoms. However, it is most preferred when (X⁵) is selectedfrom the group consisting of methyl, ethyl, propyl, butyl, and isobutyl.

[0048] In this formula (X⁶) is a halide, hydride, or alkoxide.Currently, it is preferred when (X⁶) is independently selected from thegroup consisting of fluoro and chloro. However, it is most preferredwhen (X⁶) is chloro.

[0049] In this formula “n” is a number from 1 to 3 inclusive. However,it is preferred when “n” is 3.

[0050] Examples of such compounds are as follows:

[0051] trimethylaluminum;

[0052] triethylaluminum;

[0053] tripropylaluminum;

[0054] diethylaluminum ethoxide;

[0055] tributylaluminum;

[0056] triisobutylaluminum hydride;

[0057] triisobutylaluminum; and

[0058] diethylaluminum chloride.

[0059] Currently, triethylaluminum is preferred.

[0060] The treated solid oxide compounds are compounds that have hadtheir Lewis acidity increased. It is preferred when said treated solidoxide compound comprises oxygen and at least one element selected fromthe group consisting of groups 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13,14, and 15 of the periodic table, including lanthanides and actinides(See Hawley's Condense Chemical Dictionary, 11th Edition). However, itis preferred when the element is selected from the group consisting ofAl, B, Be, Bi, Cd, Co, Cr, Cu, Fe, Ga, La, Mn, Mo, Ni, Sb, Si, Sn, Sr,Th, Ti, V, W, P, Y, Zn and Zr. It is important that these treated solidoxide compounds have electron withdrawing ability, while not wanting tobe bound by theory, it is believed that a treated solid oxide compoundshould have a higher Lewis acidity compared to the untreated solid oxidecompound. However, it is hard to accurately measure the Lewis acidity ofthese treated, and untreated solid oxide compounds so other methods havebeen used. Currently, comparing the activities of treated, and untreatedsolid oxide compounds under acid catalyzed reactions is preferred.

[0061] Treated solid oxide compounds can be produced in a variety ofways, such as, for example, by gelling, co-gelling, or impregnation ofone compound onto another, followed by calcination.

[0062] In general, it is preferred to contact at least one solid oxidecompound, such as, for example, alumina, zirconia, titania, and mixturesthereof or with mixture with other solid oxides such as, for example,silica alumina, with at least one electron-withdrawing anion sourcecompound, to form a first mixture, followed by calcining this firstmixture to form a treated solid oxide compound. In the alternative, asolid oxide compound and an electron-withdrawing anion source compoundcan be contacted and calcined simultaneously. The electron-withdrawinganion source compound is any compound that increases the Lewis acidityof the solid oxide under the conditions given herein for producing thetreated solid oxide compound. These electron-withdrawing anion sourcecompounds increase the Lewis acidity of the solid oxide by contributingto the formation of an electron withdrawing anion, such as, for example,sulfates, halides, and triflate. It should be noted that one or moredifferent electron withdrawing anions can be used.

[0063] The acidity of the solid oxide compound can be further enhancedby using two, or more, electron-withdrawing anion source compounds intwo, or more, separate contacting steps. An example of such a process iscontacting at least one solid oxide compound with a firstelectron-withdrawing anion source compound to form a first mixture,followed by calcining this first mixture, followed by contacting with asecond electron-withdrawing anion source compound to form a secondmixture, followed by calcining said second mixture to form a treatedsolid oxide compound. It should be noted that the first and secondelectron-withdrawing anion source compounds can be the same, but arepreferably different.

[0064] Suitable examples of solid oxide compounds include, but are notlimited to, Al₂O³, B₂O₃, BeO, Bi₂O₃, CdO, Co³O⁴Cr₂O₃, CuO, Fe₂O₃, Ga₂O₃,La₂, O₃Mn₂, O₃, MoO₃, NiO, P₂O₅, Sb₂O₅, SiO₂, SnO₂, SrO, ThO₂, TiO₂,V₂O₅, WO₃, Y₂O₃, ZnO, ZrO₂: and mixtures thereof, such as, for example,silica-alumina and silica-zirconia. It should be noted that solid oxidecompounds that comprise Al—O bonds are currently preferred.

[0065] It is important that the solid oxide compound is also calcined.This calcining can be conducted in an ambient atmosphere, preferably adry ambient atmosphere, at a temperature in the range of about 200° C.to about 900° C., and for a time in the range of about 1 minute to about100 hours. Currently, temperatures from about 400° C. to about 800° C.and a time in the range of about 1 hour to about 10 hours, arepreferred.

[0066] Treated solid oxide compounds, should have pore volumes greaterthan about 0.01 cc/g, preferably greater than about 0.1 cc/g, and mostpreferably, greater than about 1 cc/g.

[0067] Treated solid oxide compounds should have surface areas greaterthat about 1 m²/g, preferably greater than 100 m²/g, and most preferablygreater than 200 m²/g.

[0068] The compositions of this invention can be produced by contactingan organometal compound, an treated solid oxide compound, and anorganoaluminum compound, together. This contacting can occur in avariety of ways, such as, for example, blending. Furthermore, each ofthese compounds can be fed into the reactor separately, or variouscombinations of these compounds can be contacted together before beingfurther contacted in the reactor, or all three compounds can becontacted together before being introduced into the reactor. Currently,one method is to first contact the organometal compound and the treatedsolid oxide compound together, for about 1 minute to about 24 hours,preferably, about 1 minute to about 1 hour, at a temperature from about10° C. to about 200° C., preferably about 25° C. to about 100° C., toform a first mixture, and then contact this first mixture with anorganoaluminum compound to form the composition. During contacting. orafter contacting, the mixtures or the composition can be calcined. Thiscalcining can be conducted in an ambient atmosphere, preferably a dryambient atmosphere, at a temperature in the range of about 300° C. toabout 900° C., and for a time in the range of about 1 minute to about100 hours. Currently, temperatures from about 500° C. to about 700° C.and a time in the range of about 1 hour to about 10 hours, arepreferred. Currently, it is preferred to use dry nitrogen as the ambientatmosphere.

[0069] After contacting, the composition consists essentially of, (orconsists of) a post-contacted organometal compound, a post-contactedtreated solid oxide compound, and optionally, a post-contactedorganoaluminum compound. It should be noted that the post-contactedtreated solid oxide compound is the majority, by weight, of thecomposition. Since the exact order of contacting is not known, it isbelieved that this terminology best describes the composition'scomponents.

[0070] The composition of this invention has an activity greater than acomposition that uses the same organometal compound, and the sameorganoaluminum compound, but uses untreated Ketjen grade B alumina (seecomparative examples 4, 5, and 6) instead of the treated solid oxidecompounds of this invention. This activity is measured under slurrypolymerization conditions, using isobutane as the diluent, and with apolymerization temperature of 50-150° C., and an ethylene pressure of400-800 psig. The reactor should have substantially no indication of anywall scale, coating or other forms of fouling.

[0071] However, it is preferred if the activity is greater than 100grams polyethylene per gram of treated solid oxide compound per hour(hereafter “gP/(gS·hr)”), more preferably greater than 250, even morepreferably greater than 500, even more preferably greater than 1000 andmost preferably greater than 2000. This activity is measured underslurry polymerization conditions. using isobutane as the diluent, andwith a polymerization temperature of 90° C., and an ethylene pressure of550 psig. The reactor should have substantially no indication of anywall scale, coating or other forms of fouling.

[0072] These compositions are often sensitive to hydrogen and sometimesincorporate cornonomers well, and usually produce polymers with a lowHLMI/MI ratio.

[0073] One of the important aspects of this invention is that noaluminoxane needs to be used in order to form the composition. This alsomeans that no water is needed to help form such aluminoxanes. This isbeneficial because water can sometimes kill a polymerization process.Additionally, it should be noted that no borate compounds need to beused in order to form the composition. In summary, this means that thecomposition, which is heterogenous, and which can be used forpolymerizing monomers, can be easily and inexpensively produced becauseof the substantial absence of any aluminoxane compounds or boratecompounds. Additionally, no organochromium needs to be added, nor anyMgCl₂ needs to be added to form the invention.

[0074] The monomers useful in this invention, are unsaturatedhydrocarbons having from 2 to 20 carbon atoms. Currently, it ispreferred when the monomer is selected from the group consisting ofethylene, propylene, 1-butene, 3-methyl-1-butene, 1-pentene,3-methyl-1-pentene, 4-methyl-1-pentene, 1-hexene, 3-ethyl-1-hexene,1-heptene, 1-octene, 1-nonene, 1-decene, and mixtures thereof. However,when a homopolymer is desired, it is most preferred to use ethylene, orpropylene, as the monomer. Additionally, when a copolymer is desired, itis most preferred to use ethylene and hexene as the monomers.

[0075] Processes that can polymerize monomers into polymers are known inthe art, such as, for example, slurry polymerization, gas phasepolymerization, and solution polymerization. It is preferred to performa slurry polymerization in a loop reactor. Furthermore, it is even morepreferred to use isobutane as the diluent in a slurry polymerization.Examples of such technology can be found in U.S. Pat. Nos. 4,424,341;4,501,885; 4,613,484; 4,737,280; and 5,597,892; the entire disclosuresof which are hereby incorporated by reference.

[0076] It should be noted that under slurry polymerization conditionsthese compositions polymerize ethylene alone, or ethylene with a1-olefin, or propylene very well. In particular, the compositions usedin this process produce good quality polymer particles withoutsubstantially fouling the reactor. When the composition is to be used ina loop reactor under slurry polymerization conditions, it is preferredwhen the particle size of the solid mixed oxide compound is in the rangeof about 10 to about 1000 microns. preferably 25 to 500 microns, andmost preferably, about 50 to about 200 microns, for best control duringpolymerization.

[0077] After the polymers are produced, they can be formed into variousmanufactures, such as, for example, household containers and utensils,drums, fuel tanks, pipes, geomembranes, and liners. Various processescan form these manufactures. Usually, additives and modifiers are addedto the polymer in order to provide desired effects. It is believed thatby using the invention described herein, manufactures can be produced ata lower cost, while maintaining most, if not all, of the uniqueproperties of polymers produced with metallocene catalysts.

[0078] Additionally, these manufactures can be part of a machine, suchas, for example, a car, so that the weight of the car will be less, withthe attended benefits thereof.

EXAMPLES

[0079] These examples provide additional information to a person skilledin the art. These examples are not meant to be construed as limiting thescope of the claims.

Description of the Polymerizations Runs

[0080] All polymerization runs were conducted in a steel reactor thathad a volume of 2.2 liters. This reactor was equipped with a marinestirrer. During the polymerizations this stirrer was set to run at 400rpm. This reactor was also surrounded by a steel jacket that wasconnected to a steel condenser. The steel jacket contained methanol thatwas boiling. The boiling point of the methanol was controlled by varyingthe nitrogen pressure that was applied to the steel condenser and thesteel jacket. This control method permitted precise temperature control(±0.5° C.).

[0081] First, a treated, or untreated, solid oxide compound was charged,under nitrogen, to the reactor, which was dry. Second, organometalcompound solution was added to the reactor by syringe. Third, 0.6 litersof isobutane was charged to the reactor. Fourth, organoaluminum compoundwas added midway during the isobutane addition. Fifth, 0.6 liters ofisobutane was charged to the reactor. Sixth, ethylene was added to thereactor to equal 550 psig pressure. Seventh, the reactor was heated to90° C. This pressure was maintained during the polymerization. Duringpolymerization, stirring continued for the specified time. Activity wasdetermined by recording the flow of ethylene into the reactor tomaintain pressure. Seventh, after the specified time, the ethylene flowwas stopped and the reactor slowly depressurized. Eighth, the reactorwas opened to recover a granular polymer powder.

[0082] In all inventive runs, the reactor was clean with no indicationof any wall scale, coating or other forms of fouling. The polymer powderwas removed and weighed. Activity was specified as grams of polymerproduced per gram of treated, or untreated, solid oxide compound chargedper hour.

[0083] In some cases the treated solid oxide compound and theorganometal compound were first pre-contacted, in the reactor, for abouthalf an hour at 90° C. in one liter of isobutane before theorganoaluminum compound and ethylene were added to the reactor.

Preparation of Solid Oxides

[0084] Silica, grade 952, having a pore volume of 1.6 cc/g and a surfacearea of about 300 square meters per gram was obtained from W.R.Grace.About 10 grams of this material was placed in a 1.75 inch quartz tube,which was fitted at the bottom with a sintered quartz. While the silicawas supported on the disk, dry air was blown up through the disk at thelinear rate of about 1.6 to 1.8 standard cubic feet per hour. Anelectric furnace around the quartz tube was then turned on and thetemperature was raised at the rate of 400° C. per hour to a temperatureof 600° C. At that temperature, the silica was allowed to fluidize forthree hours in the dry air. Afterwvard, the silica was collected andstored under dry nitrogen.

[0085] Some alumina samples were also prepared by the proceduredescribed in the silica preparation. A commercial alumina sold by AKZOCompany as Ketjen grade B alumina was obtained, having a pore volume ofabout 1.78 cc/g and a surface area of around 340 square meters per gram.The temperatures used in the preparation of these aluminas were 400° C.,600° C., and 800° C.

[0086] A silica-alumina was also obtained from W.R.Grace (MS 13-110containing 13% alumina and 87% silica). This silica-alumina had a porevolume of 1.2 cc/g and a surface area of about 300 square meters pergram. This silica-alumina was prepared as described in the silicapreparation. The temperature used in the preparation of thissilica-alumina was 600° C.

[0087] A silica-titania was obtained by co-gellation as described inU.S. Pat. No. 3,887,494 (“Deitz”). Titanyl sulfate was dissolved inconcentrated sulfuric acid, to form a first mixture. Afterwards, asodium silicate solution was slowly added, with vigorous stirring, tothis first mixture, to form a second mixture. When the pH of the secondmixture reached about 6, this second mixture gelled into a homogenous,substantially-clear first product. This first product was then aged, at80° C. and a pH 7, for three hours, followed by washing it nine timeswith water, and two times in 1% ammonium nitrate, to form a secondproduct. This second product, which was a gel, was then azeotropicallydried in ethyl acetate, to form a third product. This third productcontained 8% titanium. It also had a surface area of 450 square metersper gram and a pore volume of 2.0 cc/g. This silica-titania was thenprepared as described in the silica preparation. The temperature use inthe preparation of this silica-titania was 600° C.

[0088] An alumino-phosphate was prepared according to U.S. Pat. No.4,364,855 (McDaniel). Aluminum nitrate (380 grams) and mono-ammoniumphosphate (94 grams) was dissolved in deionized water to form a firstmixture. About 170 milliliters of ammonium hydroxide was then added tothis first mixture to form a second mixture. At a pH of about 8 thissecond mixture gelled to form a first product. This first product wasthen washed twice in water, and once in n-propanol, before dryingovernight at 80° C. under a vacuum, to form a second product. Thissecond product contained a phosphorus to aluminum molar ratio of 0.8, apore volume of 2.1 cc/g,. and a surface area of 250 square meters pergram. This alumino-phosphate was then prepared as described in thesilica preparation. The temperature use in the preparation of thisalumina-phosphate was 600° C.

Comparative Examples 1-2

[0089] These examples demonstrate that an organometal compound contactedwith an organoaluminum compound, provides little, if any, polymerizationactivity.

[0090] A polymerization run was made as described earlier. First, anorganometal compound was added to the reactor (2 ml ofbis(n-butylcyclopentadienyl) zirconium dichloride solution containing0.5 grams per 100 ml of toluene). Second, half of the isobutane was thenadded to the reactor. Third, 2 ml of 15 weight percent triethyl aluminumfor example 1, or 2 ml of 25 weight percent ethyl aluminum dichloride(EADC) for example 2, were added to the reactor. Fourth, the other halfof the isobutane was added to the reactor.

[0091] Ethylene was then added to the reactor but no polymerizationactivity was observed. After one hour of contacting, the reactor wasdepressurized and opened.

[0092] In each case, no polymer was found. These results are shown inTable-I.

Comparative Examples 3-9

[0093] These examples demonstrate that contacting a solid oxidecompound, with an organometal compound, and with an organoaluminumcompound, provided little, if any, polymerization activity.

[0094] Each of the solid oxide compounds described earlier was added tothe reactor, followed by an organometal compound (2 ml ofbis(n-butylcyclopentadienyl) zirconium dichloride solution (0.5 gramsper 100 ml of toluene), and then the organoaluminum compound(triethylaluminum). These examples are shown in Table-I.

[0095] The first two examples show that contacting an organometalcompound with an organoaluminum compound provides little, if any,polymerization activity. The silica example produced almost no polymer.Alumina, which is regarded as more acidic than silica, produced morepolymer, but still the activity was very low. The alumino-phosphate,silica-alumina, and silica-titania supports exhibited only marginalactivity. Activity is expressed in Table-I as gP/(gS·hr).

Comparative Example 10

[0096] A solution was made of 244 grams of ammonium sulfate dissolved inwater to equal 437 mls total. Then 100 mls of this solution wasimpregnated onto 33.2 grams of W.R.Grace grade 952 silica. The wetmixture was dried in a vacuum oven at 110° C. for 12 hours. This isequivalent to 12.7 mmol of sulfate per gram of silica. The driedmaterial was ground through a 35 mesh screen, then calcined in air at400° C. according to the procedure described earlier. It was found tohave a pore volume of 1.22 cc/g and a surface area of 223 square metersper gram. A sample of this material was then tested for ethylenepolymerization activity as described earlier. It produced no polymer.This experiment is shown in Table II as example 10.

Examples 11-12

[0097] 122 mls of the above ammonium sulfate solution was impregnatedonto 40.6 grams of Ketjen grade B alumina. The wet mixture was dried ina vacuum oven at 110° C. for 12 hours. This is equivalent to 12.7 mmolof sulfate per gram of uncalcined alumina. The dried material was thenground through a 35 mesh screen and calcined in air at 400° C. accordingto the procedure described above. It was found to have a pore volume ofonly 0.25 cc/g and a surface area of only 38 square meters per gram. Asample of this material was then tested for ethylene polymerizationactivity as described earlier. Despite the very low porosity it stillproduced 33 g/g/h of polymer. This experiment is shown in Table II asexample 11.

[0098] This same material was then calcined again in air at 750° C. asdescribed earlier, and retested for polymerization activity. This timeit provided 583 g/g/h of polymer. This is quite remarkable consideringthe very low surface area. The polymer was found to have a melt index of0.15 and a high load melt index of 3.24. This experiment is shown inTable II as example 12.

Example 13 A, B, C

[0099] Ketjen B alumina was first calcined in air at 600° C. asdescribed earlier. Then 11.1 grams of this material was slurried with 30mls of isopropanol mixed with 1.73 grams of sulfuric acid. This isequivalent to 1.6 mmol of sulfate per gram of calcined alumina. Theisopropanol was then evaporated off under nitrogen with heat. The drysolid was then calcined in air at 550° C. as described earlier. A sampleof this material was then tested for ethylene polymerization. It yielded1387 g/g/h of polymer. This experiment is shown in Table II as example13A.

[0100] The earlier procedure Ketjen B alumina was first calcined in airat 600° C., then 5.9 grams of this material was slurried with 15 mls ofisopropanol mixed with 0.453 grams of sulfuric acid. This is equivalentto 1.6 mmol of sulfate per gram of calcined alumina. The isopropanol wasthen evaporated off under nitrogen with heat. The dry solid was thencalcined in air at 550° C. as described earlier. It was found to have apore volume of 0.93 cc/g and a surface area of 205 square meters pergram. A sample of this material was then tested for ethylenepolymerization. It yielded 324 g/g/h of polymer. This experiment isshown in Table II as example 13B.

[0101] This material was then calcined again at 800° C. for three hoursin air as described earlier. It was found to have a pore volume of 1.03cc/g and a surface area of 236 square meters per gram. It providedactivity of 58 g/g/h polymer. This experiment is shown in Table II asexample 13C.

Examples 14 A, B and 15

[0102] The procedure of example 11 was repeated except that 33.14 gramsof Ketjen B alumina was impregnated with 11.60 grams of ammonium sulfateand then it was calcined at 550C. The results of testing are shown inTable II as example 14A. During this run the sulfated alumina andmetallocene were precontacted in the reactor for 32 minutes at 90C.before other ingredients were introduced to begin the run. Polymerproduced in this run was found to have a MI of 0.21, a HLMI of 3.5,giving a shear ratio of 16.7. Gel permeation chromatography of thepolymer indicated Mw=168,000, Mn=67,900 and Mw/Mn=2.5. After calciningthe sulfated alumina was found to have a surface area of 284 squaremeters per gram and a pore volume of 0.67 cc/g and an average poreradius of 94 angstroms.

[0103] The above sulfated alumina (14A) was then calcined in air at 650Cfor three hours and tested again for polymerization. Again the sulfatedalumina and the metallocene were precontacted for 30 minutes at 90C.Details of the run are shown in Table II as example 14B. This materialwas found to have a surface area of 305 square meters per gram, a porevolume of 0.9 cc/g. and an average pore volume of 110 angstroms.

[0104] Another sample of sulfated alumina was made by the same procedureas example 14A except that 26.9 g of Ketjen B alumina was impregnatedwith 5.41 g of ammonium sulfate. Calcination was at 550C. It was foundto have a surface area of 352 square meters per gram, a pore volume of0.93 cc/g, and an average pore radius of 106 angstroms. Details of thepolymertization are given in Table II as example 15.

Comparative Example 16

[0105] A solution of 2.0 grams of concentrated sulfuric acid in 200 mlsof isopropanol was made, Ketjen B alumina was calcined in air at 600° C.as described earlier. Then 6.34 grams of this material was slurried with16 mls of the solution. This is equivalent to 0.26 mmol of sulfate pergram of calcined alumina. The isopropanol was then evaporated off undernitrogen with heat. The dry solid was then calcined in air at 500° C. asdescribed earlier. It was found to have a pore volume of 0.95 cc/g and asurface area of 213 square meters per gram. A sample of this materialwas then tested for ethylene polymerization. It yielded 6 g/g/h ofpolymer. This experiment is shown in Table II as example 16.

Example 17

[0106] A silica-alumina was obtained from W. R. Grace under thecommercial name of MS13-110. It's properties and activity have alreadybeen described earlier. It was impregnated with sulfuric acid asdescribed above in example 16 to contain 1.6 mmol sulfate per gram. Itwas then calcined in air at 600° C. as described earlier. A sample ofthis material was then charged to the reactor along with the metalloceneand isobutane and stirred for 32 minutes at 90° C. before ethylene wasadded. It yielded 82 g/g/h of polymer. This experiment is shown in TableII as example 17.

Example 18

[0107] A solution of 0.5 grams of ammonium bifluoride in 30 mls ofmethanol was added to 4.5 grams of Ketjen grade B alumina which had beencalcined in air at 600° C. as described earlier. This moistened thealumina just beyond the point of incipient wetness. This is equivalentto 3.90 mmol of fluoride per gram of calcined alumina. The methanol wasthen evaporated off under nitrogen with heat. The dry solid was thencalcined in nitrogen at 500° C. as described earlier. A sample of thismaterial was then tested for ethylene polymerization. It yielded 927g/g/h of polymer. This experiment is shown in Table III as example 18.

Examples 19-21

[0108] The procedure described in example 18 was repeated except thatthe final calcination was accomplished at 250° C., 400° C., and 600° C.Each was tested for polymerization activity and the results are shown inTable III as examples 19, 20, and 21.

Example 22

[0109] The procedure described in example 18 was repeated except thatuncalcined Ketjen B alumina was impregnated with 5.80 mmol per gram offluoride. After calcination at 500° C. it was tested for polymerizationactivity and the result are shown in Table III as example 22.

Example 23-24

[0110] W. R. Grace grade HPV alumina was calcined at 600° C. in airthree hours, giving a material of surface area around 500 square metersper gram and pore volume of about 2.8 cc/g. 3.36 grams of this materialwas heated under fluidizing nitrogen to 600° C. Then 5.0 mls ofperfluorohexane was injected into the nitrogen upstream from thealumina. Over the next 15 minutes the perfluorohexane evaporated at roomtemperature into the nitrogen and was then carried up through thefluidizing bed of alumina, where it reacted. This exposure would beequivalent to about 55 mmol of fluoride per gram of alumina if all ofthe fluoride reacted (which was obviously not the case). The aluminaturned black, presumably due to carbon deposited on it. This materialwas then tested for polymerization activity when a sample was charged tothe reactor with the metallocene at 90° C. After 30 minutes of stirring,triethyl aluminum and ethylene were added and the sample was found toprovide 1266 g/g/h of polymer. Details are shown in Table III as example23.

[0111] This material was then recalcined in air at 600° C. for threehours to burn off residual carbon. The black color turned back to white.It was then tested for polymerization activity when a sample of it wasadded to the reactor along with metallocene and triethyl aluminum,followed immediately by ethylene. It provided an activity of 2179 g/g/hof polymer. Details are shown in Table III as example 24.

Examples 25-26

[0112] Ketjen Grade B alumina was calcined in air for three hours at600° C. as described in example 5. 9.29 grams of this alumina wascharged to a dry quartz activator tube and fluidized in carbon monoxideat 600° C. Then 4.5 mls of methyl bromide was injected upstream into thecarbon monoxide. During the next 30 minutes the methyl bromide waswarmed with an electric heater causing it to evaporate and be carried bythe carbon monoxide gas through the fluidizing alumina bed at 600° C.After this treatment the alumina was black, presumably from carbondeposits. A sample was tested for polymerization activity and found togive 223 g/g/h of polymer. In a second similar run it was found to give181 g/g/h of polymer. These two runs are shown in Table IV as examples25 and 26.

Example 27

[0113] Ketjen Grade B alumina was calcined in air for three hours at600° C. as described in example 5. 9.82 grams of this alumina wascharged to a dry quartz activator tube and fluidized in carbon monoxideat 600° C. Then 1.0 mls of bromine liquid was injected upstream into thecarbon monoxide which slowly evaporated and was carried through thefluidizing alumina bed at 600° C. After this treatment the alumina waswhite. A sample was tested for polymerization activity and found to give106 g/g/h of polymer. This run is shown in Table IV as example 27.

Examples 28-31

[0114] Ten mls of Ketjen Grade B alumina was calcined in air for threehours at 600° C. as described in example 5. After this calcining step,the furnace temperature was lowered to 400° C. and 1.0 ml of carbontetrachloride was injected into the nitrogen stream and evaporatedupstream from the alumina bed. It was carried into the bed and therereacted with the alumina to chloride the surface. This is equivalent toapproximately 15.5 mmol chloride per gram of dehydrated alumina. Afterthis treatment the alumina was white. A sample was tested forpolymerization activity. In addition to the ethylene, 50 mls of 1-hexenewas also added to the reactor as a comonomer. This material gave 939g/g/h of copolymer having the following properties: melt index of 0.63,high load melt index of 10.6, shear ratio of 16.7, density of 0.9400,weight average MW of 126,000, number average MW of 50,200, andpolydispersity of 2.5. This run in shown in Table V as example 28.

[0115] This chlorided alumina was run again but without the hexene andthe details are shown in Table V as example 29. It produced 1019 g/g/hof polymer having the following properties: melt index of 0.15, highload melt index of 2.68, shear ratio of 17.9, density of 0.9493, weightaverage MW of 202,000, number average MW of 62,400, and polydispersityof 3.2.

[0116] In a similar experiment, 7.3 grams of Ketjen Grade B aluminaalready calcined at 600° C. in air, was treated with 0.37 mls of carbontetrachloride vapor in nitrogen at 400° C. This is equivalent toapproximately 2.4 mmol chloride per gram of calcined alumina. Thismaterial provided 146 g/g/h activity and is shown in Table V as example30.

[0117] In yet another similar experiment, the procedure of example 29was repeated except that 6.2 grams of 600° C. calcined alumina wastreated with 5.0 mls of carbon tetrachloride at 400° C., which isapproximately equivalent to 37.6 mmol chloride per gram. This materialyielded 1174 g/g/h activity and is shown in Table V as example 31.

Examples 32-35

[0118] Three other samples of Ketjen Grade B alumina were also calcinedat 600° C. in air as described in the above examples and then treatedwith various amounts of carbon tetrachloride at various temperatures.Table V shows the results of these experiments as examples 32, 33, and34. In example 33 the treatment was done in carbon monoxide gas insteadof nitrogen.

[0119] The catalyst of example 33 was retested for polymerizationactivity but with the following variation. Instead of charging allingredients to the reactor and immediately starting the run, the oxideand the metallocene were charged with the isobutane first and allowed tocontact each other for 37 minutes at 90° C. before the cocatalyst andethylene were added to begin the run. This run is shown in Table V asexample 35.

Example 36

[0120] W.R.Grace Grade HPV alumina was calcined in air for three hoursat 600° C., yielding a surface area of approximately 500 square metersper gram and a pore volume of about 2.8 cc/g. 5.94 grams of this aluminawas then treated with 5.0 mls of carton tetrachloride in nitrogen at600° C. Results of polymerization testing are shown in Table V asexample 36.

Example 37

[0121] W. R. Grace Grade MS 13-110 silica-alumina was calcined in airfor three hours at 600° C., as described in example 8 above. 11.2 gramsthen treated with 2.8 mls of carton tetrachloride in nitrogen at 600° C.Results of polymerization testing are shown in Table V as example 37.

Example 38

[0122] 6.96 grams of Ketjen Grade B alumina which had been calcined at400° C. in air for three hours was charged to a dry activator tube andheated under nitrogen to 400° C. 2.1 mls of silicon tetrachloride wasthen injected into the nitrogen upstream from the alumina. As itevaporated it was carried up through the alumina bed, reacting andchloriding the surface. When tested for polymerization activity thismaterial provided 579 g/g/h of polymer having a melt index of 0.20, ahigh load melt index of 3.58, and a shear ratio of 17.9. Details of thepolymerization test are shown in Table VI as example 38.

Example 39

[0123] 8.49 grams of Ketjen Grade B alumina which had been calcined at600° C. in air for three hours was charged to a dry activator tube andheated under nitrogen to 300° C. 2.8 mls of thionyl chloride was theninjected into the nitrogen upstream from the alumina. As it evaporatedit was carried up through the alumina bed, reacting and chloriding thesurface. When tested for polymerization activity this material provided764 g/g/h of polymer having a melt index of 0.13, a high load melt indexof 2.48, and a shear ratio of 18.6. Details of the polymerization testare shown in Table VI as example 39.

Example 40

[0124] 7.63 grams of Ketjen Grade B alumina which had been calcined at400° C. in air for three hours was charged to a dry activator tube andheated under dry air to 300° C. 2.55 mls of sulfuryl chloride was theninjected into the air upstream from the alumina. As it evaporated over aperiod of about 45 minutes at room temperature it was carried up throughthe alumina bed, reacting and chloriding the surface. When tested forpolymerization activity this material provided 459 g/g/h of polymerhaving a melt index of 0.101, a high load melt index of 2.83, and ashear ratio of 25.6. Details of the polymerization test are shown inTable VI as example 40.

Comparative Examples 41-43 and Examples 44-45

[0125] 2.6955 grams of solid aluminum trichloride was added to thereactor along with 2.0 mls of 15% triethyl aluminum and 2.0 mls of themetallocene solution used in previous experiments. Isobutane andethylene were added as in previous runs. However, no activity wasobserved. This run is summarized in Table 6 as example 41. Theexperiment was then repeated but with less aluminum trichloride in thereactor, but again no activity was observed. This was example 42. ThusAlCl3 itself does not function as an activator for metallocenes. Thereis a distinct difference between aluminum trichloride and chloridedalumina.

[0126] In the following example aluminum trichloride was deposited ontothe surface of dehydrated alumina in order to give it a higher surfacearea. 1.4 grams of anhydrous aluminum trichloride was dissolved in 100mls of dichloromethane. This solution was then added to 6 grams ofKetjen Grade B alumina which had been calcined at 600° C. in air forthree hours. The dichloromethane was evaporated under nitrogen at 60° C.A sample of this material was then tested for polymerization activity(example 43) but it had little. The material was then heated undernitrogen to 250° C. for one hour and retested for polymerizationactivity (example 44). This time some activity was detected. Next thematerial was again heated under nitrogen to 400° C. for one hour andretested for polymerization activity (example 45) and activity wasobserved.

Comparative Examples 46 and 48 and Example 47

[0127] In another experiment 3.5 grams of Ketjen Grade B aluminacalcined at 600° C. was treated with 10 mls of 25% ethyl aluminumdichloride (EADC) at 60° C. for 10 minutes, then rinsed twice to removeany unreacted EADC. When tested for polymerization activity (firstwithout, then with cocatalyst), none was observed (example 46). Thematerial was then heated under nitrogen for I hour at 200° C. andretested (example 47). Some activity was observed.

[0128] In a similar experiment 4.31 grams of Ketjen Grade B aluminacalcined at 400° C. was treated with 30 mls of 25 wt% diethyl aluminumchloride (DEAC) at 90° C. for 30 minutes. The excess DEAC was decantedand the solid washed three times in dry heptane. It was then dried at100° C. under nitrogen and tested for polymerization activity (example48). It exhibited 29. g/g/h activity.

Comparative Example 49

[0129] A 2.26 gram sample of Davison 952 silica which had previouslybeen calcined in dry air for three hours at 600° C. was impregnated tothe point of incipient wetness with 3.4 mls of trifluoromethane sulfonicacid (95.7% pure). The procedure was done under nitrogen in a flask.This material was then mixed with 8.96 grams of Ketjen Grade B aluminawhich had previously been calcined in dry air for three hours at 600° C.The resulting solid material was 79.9% by weight alumina, 29.1% byweight silica. This procedure was done in a dry activator tube on afluidized bed in nitrogen. The mixture was heated to 193° C.-230°C. forthree hours in nitrocen to allow the trifluoromethane sulfonic acid toevaporate and react with the alumina, which would give atriflouromethane sulfonic acid loading of 1 millimole per gram of thealumina. It was then tested for polymerization activity as describedabove except that the ethylene pressure was set at 450 psig instead of550 psig and 25 mls of 1 hexene was added to the reactor. Results areshown in Table VII.

Example 50

[0130] The solid oxide from example 49 was then heated under nitrogen to400° C. for an additional three hours to further encourage distributionand reaction of the triflic acid. It was then tested for polymerizationactivity as described above except that the ethylene pressure was set at450 psig instead of 550 psig and 25 mls of 1-hexene was added to thereactor. Results are shown in Table VII.

Example 51

[0131] The solid oxide from example 50 was again heated under nitrogento 600° C. for an additional three hours to further encouragedistribution of the triflic acid. It was then tested for polymerizationactivity as described above except that the ethylene pressure was set at450 psig instead of 550 psig and 25 mls of 1-hexene was added to thereactor. Results are shown in Table VII.

Example 52

[0132] A solution of 0.5 grams of ammonium bifluoride was dissolved in30 mls of methanol and deposited onto a 4.5 gram sample of Ketjen GradeB alumina which had been calcined at 600° C. for three hours in air.This brought the solid just beyond the point of incipient wetness. Themethanol was then evaporated off under a nitrogen purge on a hot plateand then transferred to an activator tube, where it was heated undernitrogen to 500° C. and held 2 hours. 1.89 grams of this material wasthen treated at 500C. under nitrogen with 0.5 mls of carbontetrachloride injected into the gas stream. A sample was then tested forpolymerization activity with metallocene and 2.0 mls of triethylaluminum cocatalyst. It generated 3132 g/g/h of polymer. Details arelisted in Table VIII.

Example 53-54

[0133] 6.18 grams of W.R.Grace Grade HPV alumina which had been calcinedat 600° C. for three hours in air yielding a surface area ofapproximately 500 square meters per gram and a pore volume of about 2.8cc/g, was transferred to a dry activator tube and heated under nitrogento 600° C. 0.24 mls of perfluorohexane was then injected into thenitrogen stream ahead of the furnace. The liquid evaporated and wascarried up through the alumina bed, fluoriding its surface. Then 1.55mls of carbon tetrachloride was injected into the nitrogen stream andcarried into the alumina bed at 600° C. The temperature was cooled to25° C. and the resultant fluorided-chlorided alumina was stored undernitrogen. A small sample of this material was then tested forpolymerization activity with metallocene and triethyl aluminum. Theactivity, shown in example 53, was quite high, at 4390 g/g/h.

[0134] This material was then run again except that it was allowed tostir in isobutane with the metallocene at 90° C. for 30 minutes beforethe other ingredients were added. This procedure yielded 6298 g/g/hactivity (example 54).

Example 55

[0135] Degussa Aluminoxid C, obtained by flame hydrolysis, was calcinedat 600° C. in air for three hours. Then 2.74 grams of this calcinedalumina was heated to 600° C. in air, into which 4.1 mls ofperfluorohexane was injected. As the liquid evaporated, it was carriedup by the air through the alumina bed. Afterwards the gas stream wasswitched from air to nitrogen and 1.0 ml of carbon tetrachloride wasinjected. After all had evaporated, the solid was cooled to roomtemperature and stored under dry nitrogen. A small sample was tested forpolymerization activity with metallocene and cocatalyst as previouslydescribed. This material was found to yield 1383 g/g/h. Details arerecorded in Table VIII.

Examples 56, 60-61. 63-64 and Comparative Examples 57-59

[0136] A chlorided alumina was prepared identically to that in example33. In each experiment a sample of the oxide was added to the reactorunder nitrogen, then 2 mls of a solution of 0.5 grams of bis(n-butylcyclopentadienyl) zirconium dichloride in 100 mls of toluene was added,then 0.6 liter of isobutane liquid, then 1 mmol of the cocatalyst(usually from a hexane solution) followed by another 0.6 liter ofisobutane, and finally the ethylene was added after the reactor reached90° C. Table IX shows the results of these experiments as examples 56through 62.

[0137] A similar comparison of cocatalysts was made using an aluminawhich had been fluorided rather than chlorided according to thepreparation used in example 21. These runs are shown in Table IX inexamples 63 through 66.

Examples 67-71

[0138] In each run below the fluorided chlorided alumina used in example50 was charged to the reactor, followed by 2 mls of a solution of 0.5grams of the selected metallocene in 100 mls of toluene, followed by 0.6liter of isobutane liquid, then 2.0 mils of 1M triethyl aluminum ascocatalyst, followed by another 0.6 liters of isobutane and finally theethylene. These runs were made at 90° C., like all previous runs.Details are shown in Table X. TABLE I Ex. # A¹ ° C.² S³ OAC⁴ P⁵ T⁶ A⁷ 1⁸None NA 0.0000 2 TEA 0 61.1 0 2 None NA 0.0000 2 EADC 0 28.0 0 3 Silica600 0.5686 2 TEA 0.65 63.0 1 4 Alumina 800 0.6948 1 TEA 2.7 30.7 8 5Alumina 600 0.2361 2 TEA 6.9 60.9 29  6 Alumina 400 0.8475 1 TEA trace57.2 0 7 Alumina- 600 0.8242 1 TEA 45 66.0 50  Phosphate (0.8) 8Silica-Alumina 600 0.3912 1 TEA 8.3 40.0 32  9 Silica-Titania 600 0.13922 TEA 0 60.0 0

[0139] TABLE II Ex. # A¹ S² ° C.³ S⁴ OAC⁵ P⁶ T⁷ A⁷ 10⁹ Silica 12.7 4001.3360 2 0 30.0   0 11 Alumina 12.7 400 1.5251 2 38.0 45.0  33 12Alumina 12.7 750 0.2994 2 174.5 60.0  583 13A Alumina 1.6 550 0.3474 1385.5 48.0 1387 13B Alumina 0.8 550 0.7468 2 242.0 60.0  324 13C Alumina0.8 800 0.8004 2 34.8 45.0  58 14A Alumina 2.7 550 0.0842 2 241 60 286214B Alumina 2.7 650 0.0801 2 203 60 2534 15 Alumina 1.5 550 0.0279 2 9060 3226 16 Alumina 0.26 500 0.7749 2 2.3 30.0   6 17 Silica- 1.6 6000.3318 1 19.0 42.0  82 Alumina

[0140] TABLE III Ex. # A¹ S² ° C.³ S⁴ OAC⁵ P⁶ T⁷ A⁷ 18⁹ Alumina 3.90 5000.8284 2 296.8 23.2  927 19 Alumina 3.90 250 0.2542 2 7.6 40.0  45 20Alumina 3.90 400 0.2358 2 88.1 60.0  374 21 Alumina 3.90 600 0.2253 2281.6 60.0 1250 22 Alumina 5.80 500 0.2563 1 243.9 60.0  952 23 Alumina55 500 0.2212 1 280.0 60.0 1266 24 Alumina 55 600 0.0855 1 187.5 60.52179

[0141] TABLE IV Ex. # A¹ ° C.² S³ OAC⁴ P⁵ T⁶ A⁷ 25⁸ Alumina 600 0.2612 162.0 64.0 223 26 Alumina 600 0.1688 1 38.0 74.6 181 27 Alumina 6000.2046 1 11.9 33.0 106

[0142] TABLE V Ex. # A¹ S² ° C.³ S⁴ OAC⁵ P⁶ T⁷ A⁸ 28⁹ Alumina 15.5 4000.1596 2 149.8 60.0  939 29 Alumina 15.5 400 0.1166 2 121.8 61.5 1019 30Alumina 2.4 400 0.2157 2 28.8 55.0  146 31 Alumina 37.6 400 0.1021 2123.9 62.0 1174 32 Alumina 11.7 250 0.4878 2 39.2 60.0  80 33 Alumina11.7 600 0.2058 2 351.5 63.0 1627 34 Alumina 38.2 800 0.0488 1 30.6 46.5 809 35 Alumina 11.7 600 0.1505 1 400.0 62.0 2572 36 Alumina 39.3 6000.0927 1 260.2 60.0 2807 37 Silica- 11.7 600 0.0667 1 147.8 60.5 2198Alumina

[0143] TABLE VI Ex. # A¹ Treatment S² OAC³ P⁴ T⁵ A⁶ 38⁷ Alumina SiCl4 -400° C. 0.2013 1 116.5 60.0 579 39 Alumina SOCl2 - 0.0793 1 62.0 61.4764 300° C. 40 Alumina SO2Cl2 - 0.3915 1 186.0 62.1 459 300° C. 41 noneAlCl3 solid 2.6955 2 0 30.0  0 42 none AlCl3 solid 0.0380 2 0 34.4  0 43Alumina AlCl3 - 0.4264 2 4.3 28.0  22 80° C. 44 Alumina AlCl3 - 0.3374 2135.3 60.0 401 250° C. 45 Alumina AlCl3 - 0.2335 1 74.9 60.0 322 400° C.46 Alumina EtAlCl2 - 0.8855 2 0 30.0  0 60° C. 47 Alumina EtAlCl2 -0.8943 2 122.9 49.0 168 200° C. 48 Alumina Et2AlCl - 0.4263 1 4.9 24.0 29 90° C.

[0144] TABLE VII Ex. # A¹ S² ° C.³ S⁴ OAC⁵ P⁶ T⁷ A⁸ 49 Alumina 1.0 200.0868 1 1.5 80.5  13 50 Alumina 1.0 400 .1530 1 95.1 60.5  616 51Alumina 1.0 600 .0467 1 51.1 60.2 1090

[0145] TABLE VIII EX. # A¹ Treatment S² OAC³ P⁴ R⁵ A⁶ 52⁷ Alumina F/500C& 0.2822 2 294.6 20.0 3132 Cl/500C 53 Alumina F/600C & 0.0767 2 338.460.3 4390 Cl/600C 54 Alumina F/600C & 0.0967 2 304.5 30.0 6298 Cl/600C55 Alumina F/600C & 0.1196 1 174.2 63.2 1383 Cl/600C

[0146] TABLE IX Ex. # A¹ Treatment S² CC³ P⁴ T⁵ A⁶ 56⁷ Alumina Chlorided0.1866 AlEt3 336.0 60.0 1800 57 Alumina Chlorided 0.1958 GaMe3 0 60.0  0 58 Alumina Chlorided 0.1878 ZnEt2 0 60.0   0 59 Alumina Chlorided0.1756 MgBu2 2.5 60.0  14 60 Alumina Chlorided 0.1966 AlEt2H 52.6 60.0 268 61 Alumina Chlorided 0.1777 Al(I-Bu)3 293 60.0 1649 62 AluminaChlorided 0.1840 LiHex 0 60.0   0 63 Alumina Fluorided 0.2253 AlEt3281.6 60.0 1250 64 Alumina Fluorided 0.2181 AlMe3 154.2 60.0  707 65Alumina Fluorided 0.2307 AlEt2Cl 0 40.0   0 66 Alumina Fluorided 0.2465BEt3 0 30.0   0

[0147] TABLE X Ex. # A¹ Treatment S² Metallocene⁶ P³ T⁴ A⁵ 67 AluminaF/Cl 600C 0.0212 A 141.3 63.3 6318 68 Alumina F/Cl 600C 0.0170 B 31.166.3 1656 69 Alumina F/Cl 600C 0.0213 C 15.8 64.2  693 70 Alumina F/Cl600C 0.1000 D 83.9 61.5  819

That which is claimed is:
 1. A process to produce a composition ofmatter, said process comprising contacting an organometal compound, atreated solid oxide compound, and an organoaluminum compound to producesaid composition, wherein said composition consists essentially of apost-contacted organometal compound, a post-contacted treated solidoxide compound, and optionally, a post-contacted organoaluminumcompound, and wherein said composition can polymerize ethylene into apolymer with an activity greater than a composition that uses the sameorganometal compound, and the same organoaluminum compound, but usesuntreated Ketjen grade B alumina instead of said treated solid oxidecompound, and wherein said organometal compound has the followinggeneral formula (X¹)(X²)(X³)(X⁴)M¹ wherein M is selected from the groupconsisting of titanium, zirconium, and hafnium, and wherein (X¹) isindependently selected from the group consisting of cyclopentadienyls,indenyls, fluorenyls, substituted cyclopentadienyls, substitutedindenyls, and substituted fluorenyls, and wherein said substituents onsaid substituted cyclopentadienyls, substituted indenyls, andsubstituted fluorenyls, are selected from the group consisting ofaliphatic groups, cyclic groups, combinations of aliphatic and cyclicgroups, and organometallic groups, and hydrogen; and wherein (X³) and(X⁴) are independently selected from the group consisting of halides,aliphatic groups, cyclic groups, combinations of aliphatic and cyclicgroups, and organometallic groups, and wherein (X²) is selected from thegroup consisting of Group OMC-I or Group OMC-II, and wherein saidorganoaluminun compound has the following general formula.Al(X⁵)_(n)(X⁶)_(3−n) wherein (X⁵) is a hydrocarbyl having from 1-20carbon atoms, and wherein (X⁶) is a halide, hydride, or alkoxide, andwherein “n” is a number from 1 to 3 inclusive.
 2. A process to produce acomposition of matter, said process comprising contacting an organometalcompound, a treated solid oxide compound, and an organoaluminum compoundto produce said composition, wherein said composition consistsessentially of a post-contacted organometal compound, a post-contactedtreated solid oxide compound, and optionally, a post-contactedorganoaluminum compound, and wherein said composition can polymerizeethylene into a polymer with an activity greater than 100 (gP/(gS·hr)),and wherein said organometal compound has the following general formula(X¹)(X²)(X³)(X⁴)M¹ wherein M¹ is selected from the group consisting oftitanium, zirconium, and hafnium, and wherein (X¹) is independentlyselected from the group consisting of cyclopentadienyls, indenyls,fluorenyls, substituted cyclopentadienyls, substituted indenyls, andsubstituted fluorenyls. and wherein said substituents on saidsubstituted cyclopentadienyls, substituted indenyls, and substitutedfluorenyls, are selected from the group consisting of aliphatic groups,cyclic groups, combinations of aliphatic and cyclic groups, andorganometallic groups, and hydrogen; and wherein (X³) and (X⁴) areindependently selected from the group consisting of halides, aliphaticgroups, cyclic groups, combinations of aliphatic and cyclic groups, andorganometallic groups, and wherein (X²) is selected from the groupconsisting of Group OMC-I or Group OMC-II, and wherein saidorganoaluminun compound has the following general formula.Al(X⁵)_(n)(X⁶)_(3−n) wherein (X⁵) is a hydrocarbyl having from 1-20carbon atoms, and wherein (X⁶) is a halide, hydride, or alkoxide, andwherein “n” is a number from 1 to 3 inclusive, and wherein said treatedsolid oxide compounds comprise oxygen and at least one element selectedfrom the group consisting of groups 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12,13, 14, and 15 of the periodic table, including lanthanides andactinides.
 3. A process according to claim 2 wherein said activity isgreater than
 250. 4. A process according to claim 3 wherein saidactivity is greater than
 500. 5. A process according to claim 4 whereinsaid activity is greater than
 1000. 6. A process according to claim 5wherein said activity is greater than
 2000. 7. A composition produced bythe process of claim
 2. 8. A process of using the composition of claim 7to polymerize monomers into polymers.
 9. A manufacture that comprisespolymers produced according to claim
 8. 10. A machine that comprisesmanufactures according to claim
 9. 11. A process according to claim 8wherein said polymers are produced under slurry polymerizationconditions.
 12. A process according to claim 11 wherein saidpolymerization is conducted in a loop reactor.
 13. A process accordingto claim 12 wherein said polymerization is conducted in the presence ofa diluent that comprises, in major part, isobutane.
 14. A manufacturethat comprises polymers produced according to claim
 13. 15. A machinethat comprises manufactures according to claim
 14. 16. A compositionproduced by the process of claim
 6. 17. A process of using thecomposition of claim 16 to polymerize monomers into polymers.
 18. Amanufacture that comprises polymers produced according to claim
 17. 19.A machine that comprises manufactures according to claim
 18. 20. Aprocess according to claim 17 wherein said polymers are produced underslurry polymerization conditions.
 21. A process according to claim 20wherein said polymerization is conducted in a loop reactor.
 22. Aprocess according to claim 21 wherein said polymerization is conductedin the presence of a diluent that comprises, in major part, isobutane.23. A manufacture that comprises polymers produced according to claim22.
 24. A machine that comprises manufactures according to claim
 23. 25.A process to produce a composition of matter, said process comprisingcontacting an organometal compound, a treated solid oxide compound, andan organoaluminum compound to produce said composition, wherein saidcomposition consists essentially of a post-contacted organometalcompound, a post-contacted treated solid oxide compound, and optionally,a post-contacted organoaluminum compound, and wherein said compositioncan polymerize ethylene into a polymer with an activity greater than2000 (gpl(gS·hr)), and wherein said organometal compound is selectedfrom the group consisting of bis(cyclopentadienyl) hafnium dichloride;bis(cyclopentadienyl) zirconium dichloride; [ethyl(indenyl)₂] hafniumdichloride; [ethyl(indenyl)₂] zirconium dichloride;[ethyl(tetrahydroindenyl)₂] hafnium dichloride:[ethyl(tetrahydroindenyl)₂] zirconium dichloride;bis(n-butylcyclopentadienyl ) hafnium dichloride;bis(n-butylcyclopentadienyl) zirconium dichloride;((dimethyl)(diindenyl) silane) zirconium dichloride;((dimethyl)(diindenyl) silane) hafnium dichloride;((dimethyl)(ditetrahydroindenyl) silane) zirconium dichloride;((dimethyl)(di(2-methyl indenyl)) silane) zirconium dichloride;bis(fluorenyl) zirconium dichloride, and wherein said organoaluminumcompound is selected from the group consisting of trimethylaluminum;triethylaluminum; tripropylaluminum; diethylaluminum ethoxide;tributylaluminum; triisobutylaluminum hydride; triisobutylaluminum;diethylaluminum chloride, and wherein said solid oxide compounds areselected from the group consisting of Al₂O₃, B₂O₃, BeO, Bi₂O₃, CdO,Co₃O₄, Cr₂,O₃, CuO, Fe₂O₃, Ga₂O₃, La₂O₃, Mn₂O₃, MoO₃, NiO, P₂O₅, Sb₂O₅,SiO₂, SnO₂, SrO, ThO₂, TiO₂, V₂O₅,WO₃, Y₂O₃, ZnO, ZrO₂; and mixturesthereof, and wherein said treated solid oxides have been treated withfluoride or chloride or both.